Quaternary ammonium derivatives of bisimidazoline compounds

ABSTRACT

Quaternary ammonium derivatives of bisimidazoline compounds which are characterized in having a long chain aliphatic substituent in the 2 and 2&#39;&#39; positions of the respective rings and wherein the 1, 1&#39;&#39; linking entity is an alkylene radical or polyalkylene segments internally joined by an amino or amido nitrogen atom(s). These derivatives are highly effective fabric softeners having unique physical properties.

United States Patent [1 1 McConnell Dec. 17, 1974 QUATERNARY AMMONIUMDERIVATIVES OF BISIMIDAZOLINE COMPOUNDS [75] Inventor: Robert B.McConnell, Janesville,

Wis. [73] Assignee: Ashland Oil, Inc., Ashland, Ky.

[22] Filed: July 16, 1973 [21] App]. No.: 379,574

[52] U.S. Cl. .Q 260/3095, 252/8.8 [51] Int. Cl C07d 49/34 [58] Field ofSearch 260/3096 [56] References Cited UNITED STATES PATENTS 2,846,4408/1959 Hughes....- 260/309.6

Stuart et al. 252/5 l.5 Murray ll7/6 Primary Examiner-Henry R. .lilesAssistant Examiner-C. M. S. Jaisle 5 7 ABSTRACT 14 Claims, No DrawingsQUATERNARY ONIUM DERIVATIVES OF BISIMIDAZOLINE COMPOUNDS BACKGROUND OFTHE INVENTION 1. Field of the Invention This invention relates toquaternary ammonium derivatives of a class of bisimidazolines providedby the cyclization of condensation products of certain polyalkyleneamines with fatty acids or functional equivalents thereof.

2. Description of the Prior Art Compounds containing the imidazolinering structure and further substituted in the number 2 position with along chain aliphatic group are well known in the art. These compoundsare cationic substances exhibiting surface active properties to theextent of rendering them useful cationic emulsifiers, flotation agents,corrosion inhibitors and the like. The imidazolines are of particularinterest because they can be more readily and economically prepared thanthe aliphatic amines of comparable molecular weight and functionaleffectiveness in the uses noted.

I-Ieretofore the imidazoline compounds referred to above have beenprepared by first condensing a higher fatty acid with a polyaminecontaining a secondary amine group in a gamma position with respect toat least one primary amine group. Following the foregoing step whichleads to the formation of an amido substituted alkylene amine, same iscyclized to yield the imidazoline structure. Where the cyclized productcontains a terminal primary amine group in the aliphatic residue such asthose derived, for example, from diethylene triamine, it is known thatthese compounds can be advantageously modified by further condensationwith a fatty acid.

It has also been proposed by the prior art that the quaternary ammoniumderivatives of the aforesaid imidazolines are effective fabricsofteners. As a matter of fact, a substantial proportion of the currentsofteners of commerce is of this type. Fabric softeners for householdapplications are exclusively marketed in the form of dilute aqueousdispersions thereof. Because of the viscous nature of the quaternaryammonium derivatives of the imidazolines, as well as those of thealiphatic amines mentioned hereinabove, it has proven to be difficult toprepare the dilute dispersions and even more difficult to obtain suchdispersions having requisite stability characteristics. It has,accordingly, been a continuing object of investigators in this field todevelop fabric softeners having improved dispersibility and stabilitycharacteristics with the ultimate objective in mind of developing aneffective softener which will provide a dilute aqueous dispersion havingcolloidal or pseudo soluble characteristics.

SUMMARY OF THE INVENTION In accordance with the present invention,quaternary ammonium derivatives of a class of bisimidazoline compoundsare provided wherein the indicated comwherein R is a C C hydrocarbylgroup; n is an integer of from 0-4; R is a C C alkylene group; and A ishydrogen or an acyl group of the formula R C in which R has the meaningas aforesaid.

The quatemized products of the foregoing bisimidazolines are remarkablyunusual in that the dilute aqueous dispersions thereof have theappearance of being solutions of crystal-like clarity. Dilute aqueousdispersions in contemplation of the aforesaid statement are thosecontaining from 2 to about 12 weight percent of the quatemized product.

DESCRIPTION OF THE PREFERRED I EMBODIMENTS The preparation ofimidazoline compounds of the type concerned herein basically involvesthe reaction of a higher fatty acid or functional equivalent thereofwith a polyamine. The implementation of the present invention, however,calls for the use of a specific type of polyamine. Such polyamines arethose having the following structural formula:

wherein R represents a C C alkylene group, preferably ethylene. Thepreferred polyamine is triethylenetetramine. The latter amine as well asthose otherwise corresponding to the structural formula given arecommercially available. They are reported to be prepared by theammonolysis of either an alkylene dichloride or an olefin; specificallyethylene, for realizing the preferred polyamines.

With respect to the applicable fatty acid reactants, substantially morelatitude is afforded in the selection thereof an compared to thepolyamine. Broadly, the C C fatty acids are suitable for deriving thebisimidazoline compounds useful in the practice of this invention.Representative of such fatty acids include: caproic, heptanoic,caprylic, capoic, decenoic, undecanoic, lauric, dodecenoic, tridecanoic,myristic, tetradecenoic, pentadecenoic, hexadecenoic, palmitic,heptadecenoic, stearic, oleic, nonadecanoic, eicosanoic, behemic,tetracosanoic and the like. The preferred fatty acids are the mixturesthereof derived from tallow, soybean or coconut oil. Tall oil fattyacids are exemplary of a naturally occurring mixture of acids suitablefor the instant purposes.

Particularly preferred for obtaining the contemplated bisimidazolinecompounds is the mixture of fatty acids constituting tallow. The fattyacid reactant can take the form of the fatty acid itself, an alkyl esterthereof or the naturally occurring glyceride esters. As will be notedbelow, the glyceride ester form of the fatty acid will readily split inthe course of the initial condensation of the acid and the polyaminereactant and the glycerol by-product can be removed from the reactionmixture. Since the naturally occurring glyceride form of the indicatedanimal and vegetable derived fatty acids are more economical than thefree acids or the mono esters, it is particularly preferred to use thesefatty acids in this form. In connection with this discussion of thesuitable fatty acids for use in the practice of this invention, it is tobe noted that the R substituent of the respective imidazoline ringsrepresents the hydrocarbyl group attached to the carboxyl group of thefatty acid from whence derived. Accordingly, when a mixture of fattyacids is used, such as for example, tallow, the R substituentcollectively represents the mixture of hydrocarbyl residues associatedwith carboxyl groups of said fatty acids.

In effecting the initial condensation of the fatty acid and thepolyamine such are merely heated at about 100 to 200C, preferablyemploying a nitrogen sparge when the fatty acid is in the form of thefree acid or mono ester thereof. In the case of utilizing thetriglyceride form of the fatty acid, it is preferred to carry out thecondensation at a slight pressure or under a mild reflux condition. Inpreparing the unmodified bisimidazolines contemplated herein, theselected polyamine and fatty acids are reacted in a relationship ofabout 0.9 to 1.5 moles of the polyamine for two moles of the fatty acid.Of course, when the triglyceride form of the fatty acids is used onewill employ two-thirds of a mole thereof in order to provide the twomoles of fatty acid for combining with the polyamine in the relationshipselected. As indicated, where a triglyceride oil is used, splitting toeffect the in situ formation of the polyamido amine is readilyaccomplished in the reaction system concerned. In those instances wherethe linking entity of the contemplated bisimidazolines contain one ormore secondary amine groups such can be further modified completely orpartially by reaction with a fatty acid or again a functional equivalentthereof such as a triglyceride oil. This type of further modificationcan be achieved after the cyclization step described hereinbelow orsufficient added fatty acids can be included in the initial reactionproduct in order to achieve the extent of modification desired. Thelatter procedure is preferred.

The next step in deriving the bisimidazolines involves cyclizing thepolyamido amine. This reaction is accomplished by heating the polyamidoamine at a temperature between about 125 and 250 C under vacuum.Sub-atmospheric pressure conditions in the order of from 1 to 300 mm Hgsufiice for this purpose. In those instances where the free fatty acidor a lower alkyl ester thereof is employed as a reactant, the use ofmoderate vacuum in the order indicated is generally observed. Where,however, the polyamido amine is derived from a triglyceride ester, it isadvantageous to operate at the low levels of the indicated pressurerange in order to effect the removal of the glycerine. The extent ofcyclization can be noted by analyzing for the tertiary amine content,generally referred to as the TAN value of the o reaction mixture.

Quaternization of the aforedescribed bisimidazolines can be carried outin a conventional manner. Generally, it is desirable to conduct thequatemization reaction by having the bisimidazoline in the form of aconcentrated dispersion thereof in an inert organic solvent. Suitableinert solvents include the various lower alkanols and glymes.Isopropanol is especially preferred for this purpose. The inert solventsshould be anhydrous insofar as the presence of water tends to promotehydrolysis of the imidazoline rings. The quatemization reaction can becarried out by adding a quatemizing agent to a stirred concentrate ofthe bisimidazoline. The solid contents of the concentrate for effectingthis reaction can range from about to 90 weight percent, but moreusually is about 65 to 85 percent on a weight basis. Temperaturesapplicable for this purpose range from room temperature to about 125 Cdepending upon the volatility characteristics of the inert solventemployed.

A variety of agents are useful for deriving the quaternized products. Anexemplary enumeration thereof.include: the lower alkyl chlorides andbromides, e.g., methyl chloride; the di-lower alkyl sulfates; ethylenechlorohydrin; epichlorohydrin and benzyl chloride or iodide. Thedi-lower alkyl sulfates, specifically, dimethylsulfate, represent thepreferred quatemizing agents for preparing the quaternary ammoniumcompounds contemplated herein.

Although the preferred quaternary ammonium compounds of this invention,especially those wherein the quatemizing anion is methyl sulfate, findparticular utility in fabric softening applications, other importantuses are indicated. For example, these quatemized products can also beadvantageously used in rinsing compositions for human hair, as anemulsifier for preparing oil and water emulsions, including bituminousor asphaltic materials, and as an antistatic agent for paper, fabric,polish, etc.

In order to illustrate to those skilled in the art how the presentinvention can be practiced and utilized, the following working examplesare given. As indicated, these examples are set forth solely for thepurpose of illustrating the best mode contemplated for carrying out thepresent invention. Therefore, any enumeration of details containedtherein should not necessarily be interpreted as a limitation of theinvention. The only limitation intended are those expressed in theappended claims. All parts are parts by weight unless otherwise stated.

EXAMPLE 1 Into a suitable reaction vessel equipped with a stirrer andthermometer were charged 146.24 parts (1 mole) of triethylene tetramineand 574 parts (0.667 mole) of bleached soft tallow. With stirring, thereaction mixture was heated at 150 C with a nitrogen sparge for 3 hoursto form the polyamido-amine condensation product. Following thisreaction period, the apparent molecular weight was 877 and littleunreacted triglyceride was indicated by infrared analysis. Thedi-amido-amine was then heated to ll95 C at 15 mm Hg and glycerine andwater were removed over a 2-hour period until the tertiary amine content(TAN) of the cyclization product was in excess of 90 weight percent. Theresultant bisimidazoline product was thereupon cooled to C and 590 partsthereof (0.734 mole) was dissolved in 255 parts of isopropanol.Dimethylsulfate in the amount of 185 parts (1.468 moles) was added at65-75C until the free amine content was reduced to less than 1 weightpercent. The quatemized product was bleached observing conventionalprocedure therefore, and the solids adjusted to weight percent withadded isopropanol.

EXAMPLE II The concentrate (75 wt. percent solids) of Example I in theamount of 33.3 parts was melted until completely clear and thereuponslowly added to 466.7 parts of hot tap water F) with good agitation. Theresultant dilute dispersion containing about five percent white cottontowels was placed in a household top loading washer with 35g of acommercial heavy duty detergent. The fabric load was washed in theregular warm water wash cycle, and a sufficient amount of the dilutedsoftener solution was added at the commencement of the rinse cycle toprovide 0.083 weight percent active softener based on the weight of thefabric. Following the rinse cycle, the wash load was removed and linedried at room temperature for 24 hours. The treated fabrics were thenpanel rated using an arbitrary scale of 1-4, in which 1 represents therating assigned to untreated fabric and the value 4 represents thesoftest rating; that is, the softness associated with the test fabrictreated three times with 0.3 weight percent based on cloth usingdimethyl distearyl ammonium chloride as the softener. In accordance withthis procedure, the softener product of Example I were assigned ratingsof 2.8 to 3.3. By comparison, commercial softeners usually give ratingsin the range of 2.5 to 3. Evaluation of the softener of Example I as awash cycle softener following the procedure outlined above but employinga concentration of 0.14 weight percent softener based on the fabricweight likewise showed the softener product to be excellent for thisapplication. Ratings for such application were from 2.5 to 3.0.

Rewetting was evaluated using a standard wicking test. Swatches (4 in. X2 in.) were cut from the softened towels and were suspended such thatthe edge was barely submerged in a dyed water solution. The watersolution was permitted to migrate up the swatch for a period of 6minutes. The extent of migration was then measured in millimeters.Readings for untreated towel samples averaged 75mm whereas towelstreated with dimethyl distearyl ammonium chloride gave readings in theorder of 20mm (0.083 weight percent in rinse cycle) and 5mm (0.14 weightpercent in wash cycle). In comparison, the softener product of Example Igave readings of 48mm (0.083 weight percent in rinse cycle) and 45mm(0.14 weight percent in the wash cycle).

in addition to the 5 weight percent active dispersion, other dispersionscontaining 1, 2, 3, 7, l0, and 12 weight percent active were prepared inthe manner described above. All solutions were crystal clear and werestable to the extent of exhibiting no splitting or separation after 4weeks at 70 and 105F.

EXAMPLE lll into a suitable reaction vessel equipped as in Example lwere charged 170 parts (1.16 moles) of triethylenetetramine and 580parts (0.667 mole) of refined soybean oil. With stirring the mixture washeated to 150C with a nitrogen sparge for three hours to form thepolyamido-amine condensation product. Following this reaction period,the apparent molecular weight was 750 and essentially no unreactedtriglyceride was indicated by infrared analysis. The diamidoamine wasthen heated to 160 to 195C at 15mm Hg whereupon glycerine water wereremoved over a twohour period until the tertiary amine content of thecyclization product was in excess of 85 weight percent. The resultantbisimidazoline product was cooled to 65C and 600 parts thereof (0.734mole) were dissolved in 255 parts of isopropanol. Dimethylsulfate in theamount of 185 parts (1.468 moles) was added at 65 to 75C until the freeamine content dropped to less than 2 weight percent. The quatemizedproduct was bleached observing a conventional procedure and the solidsadjusted to 75 weight percent with added isopropanol. The resultinglight colored product when following the procedure outlined in Example11 gave dilute dispersions at 1-5 wt. percent having a crystal clearappearance. The softener when used at a 0.083 weight percent activelevel based on the weight of fabric (desized towels) in the rinse cyclegave softening ratings of 2.5 to 3.0.

EXAMPLE IV Triethylenetetramine in the amount of 150 parts (1.02 moles)was reacted with 440 parts (0.667 mole) of refined coconut oil followingthe procedure outlined in Example I. The resulting dicoco bisimidazolinein the amount of 504 parts (0.75 mole) was reacted with 189 parts (1.5moles) of dimethyl sulfate at 65 to C until the free amine contentdropped to less than 1 weight percent. Upon diluting with water inaccordance with the method described in Example II, a 5 weight percentdispersion of the quatemized product exhibited crystal clear clarity.The product possessed good foaming characteristics and was found to besubstantive to human hair.

EXAMPLE V In accordance with the procedure of Example I,tetraethylenepentamine in the amount'of 189.24 parts (1 mole) wasreacted with 860 parts (1 mole) of bleached soft tallow at C for 3 hoursto provide the trialkyl arnidoamine. Following this reaction, theapparent molecular weight was 1105, and infrared analysis indicated aminimal amount of unreacted triglyceride. The triamidoamine was heatedto to C at 15mm l-lg whereupon glycerine and water were removed over a2-hour period until the tertiary amine content was in excess of 90percent. The resultant bisimidazoline in the amount of 977 parts 1 mole)was dissolved in 350 parts isopropanol and reacted with 152 parts (2moles) of dimethyl sulfate at 65 to 75C until the free amine contentdropped to less than 2 weight percent. The quatemized product wasbleached observing a conventional procedure therefore; and the solidsadjusted to 75 weight percent with added isopropanol. The resultantconcentrate provided a 2, 3, and 5 weight percent stable dispersionsexhibiting crystal clear clarity.

What is claimed is:

l. A quaternary ammonium compound having the formula:

1 .1 c c N N-' R(NA-)5- N N l l l I CH2 CH2 cH CH2 4. A compound inaccordance with claim 3 wherein A is hydrogen,

5. A compound in accordance with claim 3 wherein A is said acyl group.

6. A compound in accordance with claim 2 wherein n is 0.

7. A compound in accordance with claim 5 wherein R represents thehydrocarbyl residues of the carboxyl moiety of tallow fatty acids.

8. A compound in accordance with claim 6 wherein R represents thehydrocarbyl residues of the carboxyl moiety of tallow fatty acids.

9. A compound in accordance with claim 6 wherein R represents thehydrocarbyl residues of the carboxyl moiety of coconut fatty acids.

sulfate anion.

UNITED STATES PATENT AND TRADEMARK OFFICE QERTIFICATE 0F CORRECTIONPATENT NO. 2 3,855,235

DATED 1 December 17, 1974 INVENTORG) I Robert B. McConnell It iscertified that error appears in the above-identified patent and thatsaid Letters Patent are hereby corrected as shown below:

The formula appearing in Claim 1 at lines 50-58 should read as follows:

2 2 I l x- N--R NR) -N x- R -lc (III-I2 A (m (i-R N CH2 cH N I Theformula in column 1 at lines 61-69 should read as follows:

T 'i r CH2 CH2 CH2 CH2 Column 2, line 3, the formula reading "R -C-"should read fi This certificate supersedes Certificate of Correctionissued March 11, 1975.

Signed and Scaled this nineteenth D y of Augusf1975 [SEAL] A IleSI.

RUTH C. MASON C. MARSHALL DANN JIH'HIYIX ffice ('mnmissinnvr HI Parenlxand Trademark-x UNITED STATES PATENT OFFICE CERTIFICATE OF CCRECTIONPatent No. 5,855,335 Dated October 15, 197A Inventor) Robert B. McConnell It is certified that error appears in the above-identifiedpatent and that said'Letters Patent are hereby corrected as shown below:

The formula appearing in Claim 1 at lines 50-58 should read as shownbelow:

The formula in column 1 at lines 61-69 should read as shown below:

R R2 l I X A N R R) N x" R -C CH A CH CR H l l H N CH 35 N,

Column 2, line 3, the formula reading R -C- should read Signed andsealed, this 11 day of "March 1975.

(SEAL) Attest: A

RUTH c. MASON c. MARSHALL DAN'N Attesting Officer Commissioner ofPatents and Trademarks FORM PO-105O (10-69) USCOMM-DC 60376-P69 u 5.GOVERNMENT PRINYING OFFICE: 930

1. A QUATERNARY AMMONIUM COMPOUND HAVING THE FORMULA:
 2. A compound in accordance with claim 1 wherein R is ethylene.
 3. A compound in accordance with claim 2 wherein n is
 1. 4. A compound in accordance with claim 3 wherein A is hydrogen.
 5. A compound in accordance with claim 3 wherein A is said acyl group.
 6. A compound in accordance with claim 2 wherein n is
 0. 7. A compound in accordance with claim 5 wherein R1 represents the hydrocarbyl residues of the carboxyl moiety of tallow fatty acids.
 8. A compound in accordance with claim 6 wherein R1 represents the hydrocarbyl residues of the carboxyl moiety of tallow fatty acids.
 9. A compound in accordance with claim 6 wherein R1 represents the hydrocarbyl residues of the carboxyl moiety of coconut fatty acids.
 10. A compound in accordance with claim 6 wherein R1 represents the hydrocarbyl residues of the carboxyl group moiety of soybean fatty acids.
 11. A compound in accordance with claim 7 wherein X represents a lower alkyl sulfate anion.
 12. A compound in accordance with claim 8 wherein X represents a lower alkyl sulfate anion.
 13. A compound in accordance with claim 11 wherein R2 is methyl and X is corresponding a methyl sulfate anion.
 14. A compound in accordance with claim 12 wherein R2 is methyl and X is correspondingly a methyl sulfate anion. 